Porous organosilicate layers, and vapor deposition systems and methods for preparing same

ABSTRACT

The present invention provides porous organosilicate layers, and vapor deposition systems and methods for preparing such layers on substrates. The porous organosilicate layers are useful, for example, as masks.

BACKGROUND

Porous inorganic solids have found great utility as catalysts andseparations media for industrial applications. The openness of theirmicrostructure allows molecules access to the relatively large surfaceareas of these materials that enhance their catalytic and sorptiveactivity.

Amorphous and paracrystailine materials represent an important class ofporous inorganic solids that have been used for many years in industrialapplications. Typical examples of these materials are the amorphoussilicas commonly used in catalyst formulations and the paracrystallinetransitional aluminas used as solid acid catalysts and petroleumreforming catalyst supports. The microstructure of the silicas consistsof 100-250 Angstrom particles of dense amorphous silica, with theporosity resulting from voids between the particles. Since there is nolong range order in these materials, the pores tend be distributed overa rather large range. This lack of order also manifests itself in theX-ray diffraction pattern, which is usually featureless.

Paracrystalline materials, such as certain aluminas, also have a widedistribution of pore sizes, but tend to exhibit better defined X-raydiffraction patterns, usually consisting of a few broad peaks. Themicrostructure of these materials consists of tiny crystalline regionsof condensed alumina phases, with the porosity of the materialsresulting from irregular voids between these regions. Since, there is nolong range order controlling the sizes of pores in the material, thevariability in pore size is typically quite high. The sizes of pores inthese materials fall into a regime called the mesoporous range which,for the purposes of this application, is from about 2 to about 50nanometers (nm).

In sharp contrast to these structurally ill-defined solids are materialswhose pore size distribution is very narrow because it is controlled bythe precisely repeating crystalline nature of the materials'microstructure. These materials are called “molecular sieves”, the mostimportant examples of which are zeolites. Certain zeolitic materials areordered, porous crystalline aluminosilicates having a definitecrystalline structure as determined by X-ray diffraction, within whichthere are a large number of smaller cavities that may be interconnectedby a number of still smaller channels or pores. These cavities and poresare uniform in size within a specific zeolitic material. Since thedimensions of these pores are such as to accept for adsorption moleculesof certain dimensions while rejecting those of larger dimensions, thesematerials are known as “molecular sieves” and are utilized in a varietyof ways to take advantage of these properties. The precise crystallinemicrostructure of most zeolites manifests itself in a well-defined X-raydiffraction pattern that usually contains many sharp maxima that serveto uniquely define the material. Similarly, the dimensions of pores inthese materials are very regular, due to the precise repetition of thecrystalline microstructure. Molecular sieves typically have pore sizesin the microporous range, which is usually quoted as 0.2 nm to less than2.0 nm, with a large pore size being about 1.3 nm.

More recently, a new class of porous materials has been discovered andhas been the subject of intensive scientific research. This class of newporous materials, referred to as the M41S materials, may be classifiedas periodic mesoporous materials, which include an inorganic porouscrystalline phase material having pores larger than known zeolite porediameters, for example, diameters of 1.5 to 30 nm. The pore sizedistribution is generally uniform and the pores are regularly arranged.The pore structure of such mesoporous materials is large enough toabsorb large molecules and the pore wall structure can be as thin asabout 1 nm. Further, such mesoporous materials are known to have largespecific surface areas (e.g., 1000 m²/g) and large pore volumes (e.g., 1cc/g). For these reasons, such the mesoporous materials enable reactivecatalysts, adsorbents composed of a functional organic compound, andother molecules to rapidly diffuse into the pores and therefore, can beadvantageous over zeolites, which have smaller pore sizes. Consequently,such mesoporous materials can be useful not only for catalysis ofhigh-speed catalytic reactions, but also as large capacity adsorbents.

The preparation of periodic mesoporous materials typically requires thatthe film be spun on to the substrate. Spin on processes havedisadvantages that include, for example, the physical dimensions offilms that can be prepared by the process. Although thin films aredesired for certain applications, spin on processes typically result ina film thickness of at least 100 nm. Thus, there remains a need for newmethods of preparing periodic mesoporous films.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a method of forming a filmon a substrate (e.g., a semiconductor substrate or substrate assembly).In one embodiment, the method includes: providing a substrate; providinga vapor including at least one silsesquioxane precursor; providing avapor including at least one wetting agent or surfactant; providing atleast one reaction gas (typically water); contacting the vapor includingthe at least one silsesquioxane precursor, the vapor including the atleast one wetting agent or surfactant, and the at least one reaction gaswith the substrate to form a condensed phase on at least one surface ofthe substrate; providing a vapor including a carboxylic acid or anitrogen base; and contacting the vapor including the carboxylic acid orthe nitrogen base with the substrate having the condensed phase thereonto form a film on at least one surface of the substrate.

In another aspect, the present invention provides a method of forming afilm on a substrate. The method includes: providing a substrate in avapor deposition chamber; providing a vapor including at least onesilsesquioxane precursor; providing a vapor including at least onewetting agent or surfactant; providing at least one reaction gas(typically water); contacting the vapor including the at least onesilsesquioxane precursor, the vapor including the at least one wettingagent or surfactant, and the at least one reaction gas with thesubstrate to form a condensed phase on at least one surface of thesubstrate; agitating the substrate; providing a vapor including acarboxylic acid or a nitrogen base; and contacting the vapor includingthe carboxylic acid or the nitrogen base with the substrate having theagitated condensed phase thereon to form a film on at least one surfaceof the substrate.

In another aspect, the present invention provides an article including asubstrate having a porous organosilicate layer deposited thereon,wherein the porous organosilicate layer has a thickness of at most 100nanometers prior to removal of any organosilicate material.

In another aspect, the present invention provides a vapor depositionsystem including: a deposition chamber having a substrate positionedtherein; at least one vessel including at least one silsesquioxaneprecursor; at least one vessel including at least one wetting agent orsurfactant; at least one vessel including a carboxylic acid or anitrogen base; and a source for at least one reaction gas.

DEFINITIONS

As used herein, the term “organic group” is used for the purpose of thisinvention to mean a hydrocarbon group that is classified as an aliphaticgroup, cyclic group, or combination of aliphatic and cyclic groups(e.g., alkaryl and aralkyl groups). In the context of the presentinvention, suitable organic groups for precursors used in this inventionare those that do not interfere with the formation of the mesoporousorganosilicate using vapor deposition techniques. In the context of thepresent invention, the term “aliphatic group” means a saturated orunsaturated linear or branched hydrocarbon group. This term is used toencompass alkyl, alkenyl, and alkynyl groups, for example. The term“alkyl group” means a saturated linear or branched monovalenthydrocarbon group including, for example, methyl, ethyl, n-propyl,isopropyl, tert-butyl, amyl, heptyl, and the like. The term “alkenylgroup” means an unsaturated, linear or branched monovalent hydrocarbongroup with one or more olefinically unsaturated groups (i.e.,carbon-carbon double bonds), such as a vinyl group. The term “alkynylgroup” means an unsaturated, linear or branched monovalent hydrocarbongroup with one or more carbon-carbon triple bonds. The term “cyclicgroup” means a closed ring hydrocarbon group that is classified as analicyclic group, aromatic group, or heterocyclic group. The term“alicyclic group” means a cyclic hydrocarbon group having propertiesresembling those of aliphatic groups. The term “aromatic group” or “arylgroup” means a mono- or polynuclear aromatic hydrocarbon group. The term“heterocyclic group” means a closed ring hydrocarbon in which one ormore of the atoms in the ring is an element other than carbon (e.g.,nitrogen, oxygen, sulfur, etc.).

As a means of simplifying the discussion and the recitation of certainterminology used throughout this application, the terms “group” and“moiety” are used to differentiate between chemical species that allowfor substitution or that may be substituted and those that do not soallow for substitution or may not be so substituted. Thus, when the term“group” is used to describe a chemical substituent, the describedchemical material includes the unsubstituted group and that group withnonperoxidic O, N, S, Si, or F atoms, for example, in the chain as wellas carbonyl groups or other conventional substituents. Where the term“moiety” is used to describe a chemical compound or substituent, only anunsubstituted chemical material is intended to be included. For example,the phrase “alkyl group” is intended to include not only pure open chainsaturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl,tert-butyl, and the like, but also alkyl substituents bearing furthersubstituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl,halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, “alkyl group”includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls,hydroxyalkyls, sulfoalkyls, etc. On the other hand, the phrase “alkylmoiety” is limited to the inclusion of only pure open chain saturatedhydrocarbon alkyl substituents, such as methyl, ethyl, propyl,tert-butyl, and the like.

As used herein, “a,” “an,” “the,” and “at least one” are usedinterchangeably and mean one or more than one.

As used herein, the term “comprising,” which is synonymous with“including” or “containing,” is inclusive, open-ended, and does notexclude additional unrecited elements or method steps.

The terms “deposition process” and “vapor deposition process” as usedherein refer to a process in which a layer is formed on one or moresurfaces of a substrate (e.g., a doped polysilicon wafer) from vaporizedprecursor composition(s) including one or more silicon-containingcompounds. Specifically, one or more silicon-containing compounds arevaporized and directed to and/or contacted with one or more surfaces ofa substrate (e.g., semiconductor substrate or substrate assembly),generally placed in a deposition chamber. Typically, the substrate iscooled, and the silicon-containing compound, along with othercomponents, is condensed to give a condensed phase (e.g., a thin,uniform, silicon-containing layer) on the surface(s) of the substrate.Suitable vapor deposition processes include processes similar in natureto “chemical vapor deposition” (CVD).

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a micrograph illustrating local periodicity of a porousorganosilicate film as prepared in Example 1.

FIG. 2 is a lower magnification micrograph illustrating larger scaleperiodicity of a porous organosilicate film as prepared in Example 1.

FIG. 3 is a perspective view of a vapor deposition system suitable foruse in methods of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

A periodic mesoporous organosilica containing interconnected [Si(CH₂)]₃rings has been disclosed. See, for example, Ozin et al., Science,302:266-269 (2003). Such mesoporous organosilicates have been shown toself assemble into regular hexagonal arrays with a hole size and pitchthat could be useful, for example, as masks for nanocrystalapplications, masks for contacts, or containers in dynamic random accessmemory (DRAM) device applications. However, the disclosed preparation ofsuch periodic mesoporous materials involves spinning the film onto thesubstrate.

The present invention provides a vapor deposition method for preparingperiodic mesoporous organosilicate films. The presently disclosed vapordeposition method can be advantageous over spin on methods, for example,in that thinner films (e.g., less than 100 nm) can be provided. Further,conformal films can preferably be provided on non-planar substratesurfaces.

The method includes providing vapors of components including at leastone silsesquioxane precursor; at least one wetting agent or surfactant;and at least one reaction gas (typically water). The vapors arecontacted with a substrate to deposit (typically condensed on a cooledwafer, e.g., less than 0° C.) a condensed phase that is allowed to selfassemble. The condensed phase may optionally be agitated (e.g., treatedwith ultrasound) to promote self assembly. Such agitation can take placewithin the deposition chamber. Alternatively, the substrate with thecondensed phase thereon can be transferred to a different chamber underan inert atmosphere for agitation.

A carboxylic acid or nitrogen base can be added concurrently with,and/or subsequent to the self-assembly process. After a sufficient timefor self assembly (e.g. typically 2 to 20 hours), the materials areallowed to react and gel, typically by warming (e.g., room temperatureor above). The gelled material can then be calcined at the desiredtemperature (e.g., 130° C. or above) for 2 to 48 hours to form amesoporous organosilicate film.

Silsesquioxane precursors are silicon containing compounds used in theformation of a silsesquioxane (e.g., a mesoporous organosilicate). Asused herein, “silsesquioxanes” are polyhedral frameworks made of Si—O—Silinkages.

In one embodiment, silsesquioxane precursors include compounds of theformula (Formula II) (R¹O)₃SiR²Si(OR¹)₃, wherein each R¹ and R² isindependently an organic group, typically a C1 to C10 organic group.Preferably, each R¹ is independently a C1 to C4 aliphatic group, andmore preferably a C1 to C4 aliphatic moiety. R² is preferably a C1 toC10 divalent aliphatic moiety, and more preferably a divalent C1 to C4aliphatic moiety. Formula II can represent a wide variety ofsilsesquioxane precursors. Exemplary compounds of the formula (FormulaII) include, (CH₃O₃)₃Si(CH₂)₂Si(OCH₃)₃, (CH₃O)₃Si(OCH₃)₃,(CH₃CH₂O)₃Si(CH₂)₂Si(OCH₂CH₃)₃, (CH₃CH₂O)₃Si(CH₂)₃Si(OCH₂CH₃)₃,(CH₃O)₃Si(CH₂)₂Si(OCH₂CH₃)₃, (CH₃O)₃Si(CH₂)₃Si(OCH₂CH₃)₃ and the like,and combinations thereof.

In another embodiment, silsesquioxane precursors include cycliccompounds of the formula (Formula III) [(R¹O)₂SiC(R³)₂]_(x), whereineach R¹ is independently an organic group (typically a C1 to C10 organicgroup), each R³ is independently hydrogen or an organic group (typicallya C1 to C10 organic group), and x=3 or 4; and combinations thereof.Preferably, each R¹ is independently a C1 to C4 aliphatic group, andmore preferably a C1 to C4 aliphatic moiety. Preferably, each R³ isindependently hydrogen or a C1 to C4 aliphatic group, more preferablyhydrogen or a C1 to C4 aliphatic moiety, and most preferably hydrogen.Formula III can represent a wide variety of silsesquioxane precursors.Exemplary compounds of the formula (Formula III) include,[(CH₃O)₂SiCH₂]₃, [(CH₃CH₂O)₂SiCH₂]₃, [(CH₃O)₂SiCH₂]₄,[(CH₃CH₂O)₂SiCH₂]₄, and the like, and combinations thereof.

Further, silsesquioxane precursors can include combinations of compoundsof Formula II and compounds of Formula III.

The method also includes a component that is a wetting agent orsurfactant. As used herein, “wetting agents” and “surfactants” refer tocompounds that assist in the self assembly of the mesoporousorganosilicate. Preferably the wetting agent or surfactant hassufficient volatility to be transferred in a vapor deposition processunder typical operating conditions. A wide variety of volatilesurfactants are known in the art and typically include nonionicsurfactants. Exemplary nonionic surfactants include, for example,polyoxyalkylene compounds as disclosed, for example, in U.S. Pat. No.6,630,403 (Kramer et al.). A wide variety of wetting agents are alsoknown in the art. Exemplary wetting agents include gylcols and ethers asdisclosed, for example, in U.S. Pat. No. 6,866,799 (Orsbon et al.) andpolyols and alkoxylated alcohols as disclosed, for example, in U.S.Patent Application Publication No. 2004/0213906 A1 (Mazany et al.).Preferably the wetting agent or surfactant includes ethylene glycol orethylene glycol derivative.

In certain embodiments, the wetting agent or surfactant includes acompound of the formula (Formula I) RO(CH₂CH₂O)_(n)R, wherein each R isindependently hydrogen or an organic group (typically a C1 to C10organic group), and n is from 1 to 10. Preferably, each R isindependently a C1 to C4 aliphatic group, and more preferably a C1 to C4aliphatic moiety. Preferably n is from 1 to 4. Formula I can represent awide variety of compounds including, for example, ethylene glycol,ethylene glycol monomethyl ether, ethylene glycol dimethyl ether,diethylene glycol, diethylene glycol monomethyl ether, diethylene glycolmonobutyl ether, diethylene glycol dimethyl ether, triethylene glycol,triethylene glycol monomethyl ether, triethylene glycol dimethyl ether,tetraethyene glycol, tetraethylene glycol monomethyl ether,tetraethylene glycol dimethyl ether (i.e., tetraglyme), and the like,and combinations thereof.

The method also includes a reaction gas to react with the silsesquioxaneprecursor in forming the mesoporous organosilicate. Typically, thereaction gas is water, although peroxides could also be used for certainembodiments. In addition to being a reaction gas, water can also serveas a solvent to enhance the mobility of components during theself-assembly process.

The method further includes a component believed to facilitate thereaction between the silsesquioxane precursor and the reaction gas. Suchcomponents include, for example, carboxylic acids or nitrogen bases.

Suitable carboxylic acids are typically volatile carboxylic acids.Preferred carboxylic acids are those of the formula R⁴(CO₂H)_(x),wherein R⁴ is an organic group (typically a C1 to C10 organic group),and x=1 or 2. Preferably R⁴ is a C1 to C6 aliphatic group, and morepreferably a C1 to C6 aliphatic moiety. A wide variety of carboxylicacids can be used including, for example, acetic acid, propionic acid,butyric acid, valeric acid, malonic acid, succinic acid, andcombinations thereof.

Suitable nitrogen bases are typically volatile nitrogen bases. Preferrednitrogen bases are those of the formula R⁵R⁶R⁷N, wherein each R group isindependently hydrogen or an organic group (typically a C1 to C10organic group), and wherein two or more of R⁵, R⁶, and R⁷ can optionallyform one or more rings. Preferably each R⁵, R⁶, and R⁷ is independentlyhydrogen or a C1 to C6 aliphatic group, and more preferably hydrogen ora C1 to C6 aliphatic moiety. A wide variety of nitrogen bases can beused including, for example, ammonia, methylamine, ethylamine,ethanolamine, dimethylamine, diethylamine, diethanolamine,trimethylamine, triethylamine, triethanolamine, pyrole, pyrrolidine,piperidine, pyridine, morpholine, and combinations thereof.

The amounts of each component can be varied as desired depending on thedesired film thickness and properties. Typically, at least a 5:1 molarratio of water to silsesquioxane precursor is used. Typically, the molarratio of carboxylic acid or nitrogen base to silsesquioxane precursor is0.01 to 0.1.

The components can be vapor deposited on a substrate using vapordeposition/condensation methods known in the art. The mesoporousorganosilicate layer can be deposited, for example, on a substrate(e.g., a semiconductor substrate or substrate assembly). “Semiconductorsubstrate” or “substrate assembly” as used herein refer to asemiconductor substrate such as a base semiconductor layer or asemiconductor substrate having one or more layers, structures, orregions formed thereon. A base semiconductor layer is typically thelowest layer of silicon material on a wafer or a silicon layer depositedon another material, such as silicon on sapphire. When reference is madeto a substrate assembly, various process steps may have been previouslyused to form or define regions, junctions, various structures orfeatures, and openings such as transistors, active areas, diffusions,implanted regions, vias, contact openings, high aspect ratio openings,capacitor plates, barriers for capacitors, etc.

“Layer,” as used herein, refers to any layer that can be formed on asubstrate from one or more precursors and/or reactants according to thedeposition process described herein. The term “layer” is meant toinclude layers specific to the semiconductor industry, such as, butclearly not limited to a barrier layer, dielectric layer (i.e., a layerhaving a high dielectric constant), and conductive layer. The term“layer” is synonymous with the term “film” frequently used in thesemiconductor industry. The term “layer” is also meant to include layersfound in technology outside of semiconductor technology, such ascoatings on glass. For example, such layers can be formed directly onfibers, wires, etc., which are substrates other than semiconductorsubstrates. Further, the layers can be formed directly on the lowestsemiconductor surface of the substrate, or they can be formed on any ofa variety of layers (e.g., surfaces) as in, for example, a patternedwafer.

Various components can be used in various combinations, optionally withone or more organic solvents, to form a precursor composition.“Precursor” and “precursor composition” as used herein, refer to acomposition usable for forming, either alone or with other precursorcompositions (or reactants), a layer on a substrate assembly in adeposition process. Further, one skilled in the art will recognize thatthe type and amount of precursor used will depend on the content of alayer which is ultimately to be formed using a vapor deposition process.

The precursor compositions may be liquids or solids at room temperature(preferably, they are liquids at the vaporization temperature).Typically, they are liquids sufficiently volatile to be employed usingknown vapor deposition techniques. However, as solids they may also besufficiently volatile that they can be vaporized or sublimed from thesolid state using known vapor deposition techniques. If they are lessvolatile solids, they are preferably sufficiently soluble in an organicsolvent or have melting points below their decomposition temperaturessuch that they can be used in flash vaporization, bubbling, microdropletformation techniques, etc. As used herein, “liquid” refers to a solutionor a neat liquid (a liquid at room temperature or a solid at roomtemperature that melts at an elevated temperature). As used herein,“solution” does not require complete solubility of the solid but mayallow for some undissolved solid, as long as there is a sufficientamount of the solid delivered by the organic solvent into the vaporphase for chemical vapor deposition processing. If solvent dilution isused in deposition, the total molar concentration of solvent vaporgenerated may also be considered as a inert carrier gas.

“Inert gas” or “non-reactive gas,” as used herein, is any gas that isgenerally unreactive with the components it comes in contact with. Forexample, inert gases are typically selected from a group includingnitrogen, argon, helium, neon, krypton, xenon, any other non-reactivegas, and mixtures thereof. Such inert gases are generally used in one ormore purging processes described according to the present invention, andin some embodiments may also be used to assist in precursor vaportransport.

Solvents that are suitable for certain embodiments of the presentinvention may be, for example, one or more of the following: halogenatedhydrocarbons, silylated hydrocarbons such as alkylsilanes,alkylsilicates, ethers, polyethers, thioethers, esters, lactones,nitrites, silicone oils, or compounds containing combinations of any ofthe above or mixtures of one or more of the above. The compounds arealso generally compatible with each other, so that mixtures of variablequantities of the metal-containing compounds will not interact tosignificantly change their physical properties.

The components of the present invention can, optionally, be vaporizedand deposited substantially simultaneously with one another.Alternatively, the silicon-containing layers may be formed byalternately introducing one or more components during each depositioncycle.

Suitable substrate materials of the present invention include conductivematerials, semiconductive materials, conductive metal-nitrides,conductive metals, conductive metal oxides, etc. The substrate on whichthe silicon-containing layer is formed is preferably a semiconductorsubstrate or substrate assembly. A wide variety of semiconductormaterials are contemplated, such as for example, borophosphosilicateglass (BPSG), silicon such as, e.g., conductively doped polysilicon,monocrystalline silicon, etc. (for this invention, appropriate forms ofsilicon are simply referred to as “silicon”), for example in the form ofa silicon wafer, tetraethylorthosilicate (TEOS) oxide, spin on glass(i.e., a thin layer of SiO₂, optionally doped, deposited by a spin onprocess), TiN. TaN, W. Ru, Al, Cu, noble metals, etc. A substrateassembly may also contain a layer that includes platinum, iridium,iridium oxide, rhodium, ruthenium ruthenium oxide, strontium ruthenate,lanthanum nickelate, titanium nitride, tantalum nitride,tantalum-silicon-nitride, silicon dioxide, aluminum, gallium arsenide,glass, etc., and other existing or to-be-developed materials used insemiconductor constructions, such as dynamic random access memory (DRAM)devices, static random access memory (SRAM) devices, and ferroelectricmemory (FERAM) devices, for example.

For substrates including semiconductor substrates or substrateassemblies, the layers can be formed directly on the lowestsemiconductor surface of the substrate, or they can be formed on any ofa variety of the layers (i.e., surfaces) as in a patterned wafer, forexample.

Substrates other than semiconductor substrates or substrate assembliescan also be used in methods of the present invention. Any substrate thatmay advantageously form a metal-containing layer thereon, such as ametal oxide layer, may be used, such substrates including, for example,fibers, wires, etc.

A preferred deposition process for the present invention is a vapordeposition/condensation process. Vapor deposition processes aregenerally favored in the semiconductor industry due to the processcapability to quickly provide highly conformal layers even within deepcontacts and other openings.

The precursor compositions can be vaporized in the presence of an inertcarrier gas if desired. Additionally, an inert carrier gas can be usedin purging steps in certain process. The inert carrier gas is typicallyone or more of nitrogen, helium, argon, etc. In the context of thepresent invention, an inert carrier gas is one that does not interferewith the formation of the silicon-containing layer. Whether done in thepresence of a inert carrier gas or not, the vaporization is preferablydone in the absence of oxygen to avoid oxygen contamination of the layer(e.g., oxidation of silicon to form silicon dioxide or oxidation ofprecursor in the vapor phase prior to entry into the depositionchamber).

Suitable vapor deposition processes can be employed to form thin,continuous, uniform, silicon-containing layers onto semiconductorsubstrates. Typically one or more components are vaporized in adeposition chamber and directed to and/or contacted with the substrateto form a silicon-containing layer on the substrate. It will be readilyapparent to one skilled in the art that the vapor deposition process maybe enhanced by employing various related techniques such as plasmaassistance, photo assistance, laser assistance, as well as othertechniques.

A typical vapor deposition process may be carried out in a chemicalvapor deposition reactor, such as a deposition chamber available underthe trade designation of 7000 from Genus, Inc. (Sunnyvale, Calif.), adeposition chamber available under the trade designation of 5000 fromApplied Materials, Inc. (Santa Clara, Calif.), or a deposition chamberavailable under the trade designation of Prism from Novelus, Inc. (SanJose, Calif.). However, any deposition chamber suitable for performingvapor deposition may be used.

Several modifications of the CVD chambers are possible, for example,using atmospheric pressure chemical vapor deposition, low pressurechemical vapor deposition (LPCVD), plasma enhanced chemical vapordeposition (PECVD), hot wall or cold wall reactors or any other chemicalvapor deposition technique. Furthermore, pulsed CVD can be used, whichis similar to ALD but does not rigorously avoid intermixing of precursorand reactant gas streams.

Preferred thicknesses of the mesoporous organosilcate layers of thepresent invention are at least 1 angstrom (Å), more preferably at least5 Å, and more preferably at least 10 Å. Additionally, preferred filmthicknesses are typically no greater than 100 nm, more preferably nogreater than 50 nm, and more preferably no greater than 20 nm.

When components are introduced by pulsing, the pulse duration ofprecursor composition(s) and inert carrier gas(es) is generally of aduration sufficient to saturate the substrate surface. Typically, thepulse duration is at least 0.1, preferably at least 0.2 second, and morepreferably at least 0.5 second. Preferred pulse durations are generallyno greater than 5 seconds, and preferably no greater than 30 seconds.

For a typical vapor deposition process, the pressure inside thedeposition chamber is at least 10⁻⁸ torr (1.3×10⁻⁶ Pa), preferably atleast 10⁻⁷ torr (1.3×10⁻⁵ Pa), and more preferably at least 10⁻⁶ torr(1.3×10⁻⁴ Pa). Further, deposition pressures are typically no greaterthan 10 torr (1.3×10³ Pa), preferably no greater than 1 torr (1.3×10²Pa), and more preferably no greater than 10⁻¹ torr (13 Pa). Typically,the deposition chamber is purged with an inert carrier gas after thevaporized precursor composition(s) have been introduced into the chamberand/or reacted for each cycle. The inert carrier gas/gases can also beintroduced with the vaporized precursor composition(s) during eachcycle.

The calcining (or annealing) operation is preferably performed for atime period of at least 0.5 minute, more preferably for a time period ofat least 1 minute. Additionally, the annealing operation is preferablyperformed for a time period of no greater than 48 hours, and morepreferably for a time period of no greater than 24 hours.

One skilled in the art will recognize that such temperatures and timeperiods may vary. For example, furnace anneals and rapid thermalannealing may be used, and further, such anneals may be performed in oneor more annealing steps.

As stated above, porous organosilicate films, and especially mesoporousorganosilicate films and periodic mesoporous organosilicate films, canbe used in semiconductor processes as, for example, etch masks and/ordeposition masks. Such porous organosilicate films can also be used togenerate nanocrystals, contacts, or containers (e.g., deep holes ascylindrical containers).

A system that can be used to perform vapor deposition processes of thepresent invention is shown in FIG. 3. The system includes an enclosedvapor deposition chamber 10, in which a vacuum may be created usingturbo pump 12 and backing pump 14. One or more substrates 16 (e.g.,semiconductor substrates or substrate assemblies) are positioned inchamber 10. A constant nominal temperature is established for substrate16, which can vary depending on the process used. Substrate 16 may becooled, for example, to temperatures as low as −100° C. or lower byactivating cooling loop 19. Cooling loop 19 can employ conventionalcoolants known in the art (e.g., fluorocarbon coolants in a closed cyclerefrigerator, liquid nitrogen, and the like). Substrate 16 may also beheated, for example, by an electrical resistance heater 18 on whichsubstrate 16 is mounted. Other known methods of heating the substratemay also be utilized.

In this process, precursor compositions as described herein, 60 and/or61, are stored in vessels 62. The precursor composition(s) are vaporizedand separately fed along lines 64 and 66 to the deposition chamber 10using, for example, an inert carrier gas 68. A reaction gas 70 may besupplied along line 72 as needed. Also, a purge gas 74, which is oftenthe same as the inert carrier gas 68, may be supplied along line 76 asneeded. As shown, a series of valves 80-85 are opened and closed asrequired.

The following examples are offered to further illustrate variousspecific embodiments and techniques of the present invention. It shouldbe understood, however, that many variations and modificationsunderstood by those of ordinary skill in the art may be made whileremaining within the scope of the present invention. Therefore, thescope of the invention is not intended to be limited by the followingexample. Unless specified otherwise, all percentages shown in theexamples are percentages by weight.

EXAMPLES Example 1 Vapor Deposition of a Silsesquioxane PrecursorCompound of Formula III (R¹=ethyl; R³=hydrogen; and x=3) to Form aPorous Organosilicate Layer

A layer was deposited on a bare silicon wafer as follows.Tris(diethoxysila)cyclohexane was condensed at −40° C. on acryogenically cooled wafer (approximately −20° C. to −40° C.) at apressure of 4×10⁻⁶ torr using a 2 second pulse. Water was used as areaction gas and/or solvent, and was pulsed in from a fixed volumesaturated with room temperature water vapor to result in a pressure of1.3×10⁻⁵ torr. Tetraglyme at 70° C. was pulsed in for 1 second. Thecycle was then repeated an additional number of times to yield thedesired thickness of the film. The wafer was moved from the chamber toanother wafer stage at approximately 5° C. in an inert atmosphere, andsubjected to ultrasonic agitation to promote self-assembly in the film.The wafer was then returned to the deposition chamber at atmosphericpressure under an inert atmosphere and allowed to cool and freeze at−40° C. The pressure in the chamber was then reduced to 4×10⁻⁶ torr.Glacial acetic acid was pulsed in from a fixed volume to result in apressure of 7×0-5 torr. The wafer was then warmed to room temperatureunder nitrogen at atmospheric pressure to allow the film to gel. Thewafer was then calcined at 200° C. for 1 hour. Transmission electronmicroscopy (TEM) on the resulting film resulted in the micrographsillustrated in FIGS. 1 and 2, which illustrate self-assembly of thefilm. FIG. 1 is a micrograph illustrating local periodicity (e.g., inapproximately a 3 micrometer range) of the film. FIG. 2 is a lowermagnification micrograph illustrating periodicity or self-assembly on alarger scale.

The complete disclosures of the patents, patent documents, andpublications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousmodifications and alterations to this invention will become apparent tothose skilled in the art without departing from the scope and spirit ofthis invention. It should be understood that this invention is notintended to be unduly limited by the illustrative embodiments andexamples set forth herein and that such examples and embodiments arepresented by way of example only with the scope of the inventionintended to be limited only by the claims set forth herein as follows.

1-28. (canceled)
 29. An article comprising a substrate having a porousorganosilicate layer deposited thereon, wherein the porousorganosilicate layer has a thickness of at most 100 nanometers prior toremoval of any organosilicate material.
 30. The article of claim 29wherein the wherein the porous organosilicate layer has a thickness ofat most 100 nanometers prior to removal of any organosilicate materialby a mechanical planarization process.
 31. The article of claim 29wherein the wherein the porous organosilicate layer has a thickness ofat most 100 nanometers prior to removal of any organosilicate materialby a chemical mechanical planarization process.
 32. The article of claim29 wherein the substrate is a semiconductor substrate or substrateassembly.
 33. The article of claim 29 wherein the porous organosilicatelayer is formed by a method comprising a vapor deposition process. 34.The article of claim 29 wherein the vapor deposition process is a vapordeposition/condensation process.
 35. A vapor deposition systemcomprising: a deposition chamber having a substrate positioned therein;at least one vessel comprising at least one silsesquioxane precursor; atleast one vessel comprising at least one wetting agent or surfactant; atleast one vessel comprising a carboxylic acid or a nitrogen base; and asource for at least one reaction gas.
 36. A method of forming a film ona substrate, the method comprising: contacting a substrate with: a vaporcomprising at least one silsesquioxane precursor; a vapor comprising atleast one wetting agent or surfactant; and at least one reaction gas; toform a condensed phase on at least one surface of the substrate; andcontacting a vapor comprising a carboxylic acid or a nitrogen base withthe substrate having the condensed phase thereon to form an at leastpartially self-assembled film on at least one surface of the substrate.37. The method of claim 36 further comprising agitating the substrateprior to contacting the vapor comprising the carboxylic acid or thenitrogen base with the substrate having the condensed phase thereon. 38.The method of claim 36 wherein contacting the vapor comprising thecarboxylic acid or the nitrogen base with the substrate having thecondensed phase thereon allows the condensed phase to gel upon heating.39. The method of claim 36 further comprising heating the condensedphase to form a gel.
 40. The method of claim 39 wherein the gel is atleast partially self-assembled.
 41. The method of claim 39 furthercomprising calcining the gel to form a porous organosilicate layer onthe at least one surface of the substrate.
 42. The method of claim 41wherein the porous organosilicate layer is a mesoporous organosilicate.43. The method of claim 42 wherein the porous organosilicate layer is aperiodic mesoporous organosilicate.
 44. A method of forming a film on asemiconductor substrate or substrate assembly, the method comprising:contacting a semiconductor substrate or substrate assembly with: a vaporcomprising the at least one silsesquioxane precursor; a vapor comprisingthe at least one wetting agent or surfactant; and at least one reactiongas; to form a condensed phase on at least one surface of thesemiconductor substrate or substrate assembly; and contacting a vaporcomprising a carboxylic acid or a nitrogen base with the semiconductorsubstrate or substrate assembly having the condensed phase thereon toform an at least partially self-assembled film on at least one surfaceof the semiconductor substrate or substrate assembly.
 45. The method ofclaim 44 wherein the silsesquioxane precursor is selected from the groupconsisting of compounds of the formula (Formula II) (R¹O)₃SiR²Si(OR¹)₃,wherein each R¹ and R² is independently an organic group; cycliccompounds of the formula (Formula III) [(R¹O)₂SiC(R³)₂]_(x), whereineach R¹ is independently an organic group, each R³ is independentlyhydrogen or an organic group, and x=3 or 4; and combinations thereof.46. The method of claim 44 wherein the at least one wetting agent orsurfactant comprises a compound of the formula (Formula I)RO(CH₂CH₂O)_(n)R, wherein each R is independently hydrogen or an organicgroup, and n is from 1 to
 10. 47. The method of claim 44 wherein the atleast one reaction gas comprises water.
 48. The method of claim 44wherein the carboxylic acid is a volatile carboxylic acid of the formulaR⁴(CO₂H)_(x), wherein R⁴ is an organic group and x=1 or
 2. 49. Themethod of claim 44 wherein the nitrogen base is a volatile nitrogen baseof the formula R⁵R⁶R⁷N, wherein each R group is independently hydrogenor an organic group, and wherein two or more of R⁵, R⁶, and R⁷ canoptionally form one or more rings.
 50. A method of forming a film on asubstrate, the method comprising: contacting a substrate in a vapordeposition chamber with: a vapor comprising at least one silsesquioxaneprecursor; a vapor comprising at least one wetting agent or surfactant;and at least one reaction gas; to form a condensed phase on at least onesurface of the substrate; agitating the substrate; and contacting avapor comprising a carboxylic acid or a nitrogen base with the substratehaving the agitated condensed phase thereon to form an at leastpartially self-assembled film on at least one surface of the substrate.51. The method of claim 50 wherein the substrate is agitated in thevapor deposition chamber.
 52. The method of claim 50 wherein thesubstrate is agitated in a different chamber.
 53. The method of claim 50wherein agitating the substrate comprises treating the substrate withultrasound.